Microbicides

ABSTRACT

α-Amino acid amides of the formula I ##STR1## in which n is the number zero or one; 
     R 1  is C 1  -C 12  alkyl, which is unsubstituted or can be substituted by C 1  -C 4  alkoxy, C 1  -C 4  alkylthio, C 1  -C 4  alkylsulfonyl, C 3  -C 8  cycloalkyl, cyano, C 1  -C 6  alkoxycarbonyl, C 3  -C 6  alkenyloxycarbonyl or C 3  -C 6  alkynyloxycarbonyl; C 3  -C 8  cycloalkyl; C 2  -C 12  alkenyl; C 2  -C 12  alkynyl; C 1  -C 12  halogenoalkyl or a group NR 13  R 14  ; in which 
     R 13  and R 14  independently of one another are hydrogen or C 1  -C 6  alkyl or together are tetra- or pentamethylene; 
     R 2  and R 3  independently of one another are hydrogen; C 1  -C 8  alkyl; C 1  -C 8  alkyl which is substituted by hydroxyl, C 1  -C 4  alkoxy, mercapto or C 1  -C 4  alkylthio; C 3  -C 8  alkenyl; C 3  -C 8  alkynyl; C 3  -C 8  cycloalkyl or C 3  -C 8  cycloalkyl-C 1  -C 4  alkyl, or in which the two groups R 2  and R 3 , together with the carbon atom to which they are bonded, form a three- to eight-membered carbocyclic ring; 
     R 4  is hydrogen or C 1  -C 6  alkyl; 
     R 5  is hydrogen; C 1  -C 6  alkyl or phenyl, which is unsubstituted or can be substituted by halogen, nitro, C 1  -C 4  alkyl, C 1  -C 4  halogenoalkyl, C 1  -C 4  alkoxy or C 1  -C 4  alkylthio; and 
     R 6  is a group G ##STR2## in which R 7  and R 8  independently of one another are hydrogen or C 1  -C 6  alkyl; 
     p is the number zero or one; and 
     R 9 , R 10  and R 11  independently of one another are hydrogen, C 1  -C 6  alkyl, C 1  -C 6  halogenoalkyl, C 3  -C 6  alkenyl, C 3  -C 6  alkynyl, C 1  -C 6  alkoxy, C 3  -C 6  alkenyloxy, C 3  -C 6  alkynyloxy, C 1  -C 6  alkylthio, halogen or nitro are valuable microbicides. They can be employed in crop protection in the form of suitable compositions, for example for controlling fungal diseases.

The present invention relates to novel α-amino acid amides of thefollowing formula I. It relates to the preparation of these substancesand to agrochemical compositions which comprise at least one of thesecompounds as the active ingredient. The invention also relates to thepreparation of the compositions mentioned and to the use of the activeingredients or compositions for controlling or preventing infestation ofplants by phytopathogenic microorganisms, preferably fungi.

The compounds according to the invention are those of the generalformula I ##STR3## in which the substituents are defined as follows: nis the number zero or one;

R₁ is C₁ -C₁₂ alkyl, which is unsubstituted or can be substituted by C₁-C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfonyl, C₃ -C₈ cycloalkyl,cyano, C₁ -C₆ alkoxycarbonyl, C₃ -C₆ alkenyloxycarbonyl or C₃ -C₆alkynyloxycarbonyl; C₃ -C₈ cycloalkyl; C₂ -C₁₂ alkenyl; C₂ -C₁₂ alkynyl;C₁ -C₁₂ halogenoalkyl or a group NR₁₃ R₁₄ ; in which

R₁₃ and R₁₄ independently of one another are hydrogen or C₁ -C₆ alkyl ortogether are tetra- or pentamethylene;

R₂ and R₃ independently of one another are hydrogen; C₁ -C₈ alkyl; C₁-C₈ alkyl which is substituted by hydroxyl, C₁ -C₄ alkoxy, mercapto orC₁ -C₄ alkylthio; C₃ -C₈ alkenyl; C₃ -C₈ alkynyl; C₃ -C₈ cycloalkyl orC₃ -C₈ cycloalkyl-C₁ -C₄ alkyl, or in which the two groups R₂ and R₃,together with the carbon atom to which they are bonded, form a three- toeight-membered carbocyclic ring;

R₄ is hydrogen or C₁ -C₆ alkyl;

R₅ is hydrogen; C₁ -C₆ alkyl or phenyl, which is unsubstituted or can besubstituted by halogen, nitro, C₁ -C₄ alkyl, C₁ -C₄ halogenoalkyl, C₁-C₄ alkoxy or C₁ -C₄ alkylthio; and

R₆ is a group G ##STR4## in which R₇ and R₈ independently of one anotherare hydrogen or C₁ -C₆ alkyl;

p is the number zero or one; and

R₉, R₁₀ and R₁₁ independently of one another are hydrogen, C₁ -C₆ alkyl,C₁ -C₆ halogenoalkyl, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₁ -C₆ alkoxy, C₃-C₆ alkenyloxy, C₃ -C₆ alkynyloxy, C₁ -C₆ alkylthio, halogen or nitro.

An important group is formed by compounds of the formula I in which

n is the number zero or one;

R₁ is C₁ -C₁₂ alkyl; C₁ -C₁₂ alkyl which is substituted by C₁ -C₄alkoxy, C₁ -C₄ alkylthio or C₁ -C₄ alkylsulfonyl; C₂ -C₁₂ alkenyl; C₂-C₁₂ alkynyl; C₁ -C₁₂ halogenoalkyl or a group NR₁₃ R₁₄ ; in which

R₁₃ and R₁₄ independently of one another are C₁ -C₆ alkyl or togetherare tetra- or pentamethylene;

R₂ and R₃ independently of one another are hydrogen; C₁ -C₈ alkyl; C₁-C₈ alkyl which is substituted by hydroxyl, C₁ -C₄ alkoxy, mercapto orC₁ -C₄ alkylthio; C₃ -C₈ alkenyl; C₃ -C₈ alkynyl; C₃ -C₈ cycloalkyl; orC₃ -C₈ cycloalkyl-C₁ -C₄ alkyl, or in which the two groups R₂ and R₃,together with the carbon atom to which they are bonded, form a three- toeight-membered carbocyclic ring;

R₄ is hydrogen or C₁ -C₆ alkyl;

R₅ is hydrogen; C₁ -C₆ alkyl or phenyl, which is unsubstituted orsubstituted by halogen, nitro, C₁ -C₄ alkyl, C₁ -C₄ halogenoalkyl, C₁-C₄ alkoxy or C₁ -C₄ alkylthio; and

R₆ is a group G: ##STR5## in which R₇ and R₈ independently of oneanother are hydrogen or C₁ -C₆ alkyl;

p is the number zero or one; and

R₉, R₁₀ and R₁₁ independently of one another are hydrogen, C₁ -C₆ alkyl,C₁ -C₆ halogenoalkyl, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₁ -C₆ alkoxy, C₃-C₆ alkenyloxy, C₃ -C₆ alkynyloxy, C₁ -C₆ alkylthio, halogen or nitro(sub-group A).

An important group is formed by compounds of the formula I in which

n is the number zero or one and

R₁ is C₁ -C₁₂ alkyl; C₁ -C₁₂ alkyl which is substituted by C₁ -C₄alkoxy, C₁ -C₄ alkylthio or C₁ -C₄ alkylsulfonyl; C₂ -C₁₂ alkenyl; C₁-C₁₂ halogenoalkyl or a group NR₁₃ R₁₄ ; in which

R₁₃ and R₁₄ independently of one another are C₁ -C₆ alkyl, or R₁₃ andR₁₄ together are tetra- or pentamethylene;

R₂ is hydrogen;

R₃ is C₁ -C₈ alkyl; C₁ -C₈ alkyl which is substituted by hydroxyl, C₁-C₄ alkoxy, mercapto or C₁ -C₄ alkylthio; or C₃ -C₈ cycloalkyl;

R₄ is hydrogen;

R₅ is phenyl, which is unsubstituted or substituted by halogen, nitro,C₁ -C₄ alkyl, C₁ -C₄ halogenoalkyl, C₁ -C₄ alkoxy or C₁ -C₄ alkylthioand

R₆ is a group G in which

p is the number zero; and

R₉, R₁₀ and R₁₁ independently of one another are hydrogen, C₁ -C₆ alkyl,C₁ -C₆ halogenoalkyl, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆alkynyloxy, halogen or nitro (sub-group B).

Compounds of the formula I which are of particular importance are thosein which

n is the number zero or one;

R₁ is C₁ -C₁₀ alkyl; C₁ -C₄ halogenoalkyl; C₂ -C₆ alkenyl; C₅ -C₆cycloalkyl; C₁ -C₆ alkyl which is substituted by cyano or C₁ -C₄alkoxycarbonyl, or C₁ -C₂ dialkylamino;

R₂ is hydrogen;

R₃ is C₂ -C₅ alkyl or C₃ -C₆ cycloalkyl;

R₄ is hydrogen;

R₅ is phenyl, which is unsubstituted or substituted by halogen; and

R₆ is a group G, in which

p is the number zero;

R₉ is hdyrogen; and

R₁₀ and R₁₁ independently of one another are hydrogen or halogen(sub-group AA).

Another important group is formed by compounds of the formula I in which

n is the number zero or one and

R₁ is C₁ -C₁₀ alkyl; C₁ -C₄ halogenoalkyl; C₂ -C₆ alkenyl, or C₁ -C₂dialkylamino;

R₂ is hydrogen;

R₃ is C₂ -C₅ alkyl or C₃ -C₆ cycloalkyl;

R₄ is hydrogen;

R₅ is phenyl, which is unsubstituted or substituted by halogen, and

R₆ is a group G in which

p is the number zero;

R₉ is hydrogen; and

R₁₀ and R₁₁ independently of one another are hydrogen or halogen(sub-group C).

Among these compounds, those in which n is the number one are preferred(sub-group Ca).

Compounds of sub-group C which are also preferred are those in which

n has the value one and

R₃ is C₃ -C₄ alkyl (sub-group Cd).

Important compounds of the sub-group AA within the scope of formula Iare those in which

n has the value one; and

R₁ is methyl, ethyl, vinyl, cyclopentyl, cyclohexyl or dimethylamino(sub-group AAa).

Another preferred group is formed by compounds of the formula I in which

R₁ is C₁ -C₁₂ alkyl; C₃ -C₈ cycloalkyl; C₁ -C₁₂ alkyl which issubstituted by C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄ alkylsulfonyl, C₃-C₈ cycloalkyl, cyano, C₁ -C₆ alkoxycarbonyl, C₃ -C₆ alkenyloxycarbonylor C₁ -C₆ alkynyloxycarbonyl; C₂ -C₁₂ alkenyl; C₁ -C₁₂ halogenoalkyl ora group NR₁₃ R₁₄ ; in which

R₁₃ and R₁₄ independently of one another are hydrogen or C₁ -C₆ alkyl ortogether are tetra- or pentamethylene;

R₂ is hydrogen;

R₃ is C₁ -C₈ alkyl; C₁ -C₈ alkyl which is substituted by hydroxyl, C₁-C₄ alkoxy, mercapto or C₁ -C₄ alkylthio; or C₃ -C₈ cycloalkyl;

R₄ is hdyrogen or C₁ -C₄ alkyl;

R₅ is hydrogen; or C₁ -C₆ alkyl; and

R₆ is a group G in which

R₇ and R₈ independently of one another are hydrogen or C₁ -C₄ alkyl;

p is the number one; and

R₉, R₁₀ and R₁₁ independently of one another are hydrogen, C₁ -C₆ alkyl,C₁ -C₆ halogenoalkyl, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆alkynyloxy or halogen (sub-group F).

Important compounds of sub-group C within the scope of formula I arethose in which

n is the number one and

R₁ is methyl; ethyl; vinyl or dimethylamino (sub-group Cc).

An important sub-group is formed by compounds of the formula I in which

n is the number zero or one and

R₁ is C₁ -C₁₂ alkyl; C₁ -C₁₂ alkyl which is substituted by C₁ -C₄alkoxy, C₁ -C₄ alkylthio or C₁ -C₄ alkylsulfonyl; C₂ -C₁₂ alkenyl; C₁-C₁₂ halogenoalkyl or a group NR₁₃ R₁₄ ; in which

R₁₃ and R₁₄ independently of one another are C₁ -C₆ alkyl or togetherare tetra- or pentamethylene;

R₂ is hydrogen;

R₃ is C₁ -C₈ alkyl; C₁ -C₈ alkyl which is substituted by hydroxyl, C₁-C₄ alkoxy, mercapto or C₁ -C₄ alkylthio; or C₃ -C₈ cycloalkyl;

R₄ is hydrogen or C₁ -C₄ alkyl;

R₅ is hydrogen or C₁ -C₆ alkyl and

R₆ is a group G in which

R₇ and R₈ independently of one another are hydrogen or C₁ -C₄ alkyl;

p is the number one; and

R₉, R₁₀ and R₁₁ independently of one another are hydrogen, C₁ -C₆ alkyl,C₁ -C₆ halogenoalkyl, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆alkynyloxy or halogen (sub-group D).

A preferred sub-group is formed by compounds of the formula I in which nis the number zero or one and the other substituents are defined asfollows:

R₁ is C₁ -C₁₀ alkyl, C₁ -C₄ halogenoalkyl, C₂ -C₆ alkenyl or C₁ -C₂dialkylamino;

R₂ is hydrogen;

R₃ is C₂ -C₅ alkyl or C₃ -C₆ cycloalkyl;

R₄ is hydrogen or C₁ -C₄ alkyl;

R₅ is hydrogen; and

R₆ is a group G in which

R₇ is hydrogen;

R₈ is hydrogen or C₁ -C₄ alkyl;

p is the number one; and

R₉, R₁₀ and R₁₁ independently of one another are hydrogen, C₁ -C₆ alkyl,C₁ -C₆ halogenoalkyl, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆alkynyloxy or halogen (sub-group E).

Preferred compounds of sub-group E are those in which

n is the number one,

R₁ is C₁ -C₁₀ alkyl, C₁ -C₄ halogenoalkyl, C₂ -C₄ alkenyl or C₁ -C₂dialkylamino;

R₉ is hydrogen; and

R₁₀ and R₁₁ are C₁ -C₆ alkoxy (sub-group Ea).

In this particularly preferred sub-group Ea, particular compounds of theformula I are those in which

R₁ is C₁ -C₄ alkyl, C₁ -C₄ halogenoalkyl, vinyl or dimethylamino(sub-group Eab).

In the preferred sub-group Ea, compounds of the formula I which arefurthermore preferred are those in which

R₃ is C₃ -C₄ alkyl (sub-group Eaa).

Further preferred compounds of sub-group Ea are compounds of the formulaI in which

R₄ is hydrogen; and

R₆ is a group G in which

R₇ and R₈ are hydrogen;

p is the number one;

R₉ is hydrogen; and

R₁₀ and R₁₁ are C₁ -C₆ alkoxy (sub-group Eac).

In the particularly preferred sub-group Ea, preferred compounds of theformula I are those in which

R₁₀ is C₁ -C₄ alkoxy in the p-position and

R₁₁ is C₁ -C₄ alkoxy in the m-position (sub-group Ead).

Preferred compounds of sub-group Ead within the scope of the formula Iare those in which

R₁ is C₁ -C₄ alkyl; vinyl or dimethylamino;

R₁₀ is p-methoxy; and

R₁₁ is m-methoxy (sub-group Eada).

Important compounds within the scope of the formula I are those in which

n is the number one; and

R₁ is C₁ -C₁₀ alkyl; C₁ -C₄ halogenoalkyl; C₂ -C₄ alkenyl; C₅ -C₆cycloalkyl; C₁ -C₄ alkyl which is substituted by cyano or C₁ -C₄alkoxycarbonyl, or C₁ -C₂ dialkylamino;

R₉ is hydrogen; and

R₁₀ and R₁₁ are C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy or C₃ -C₆ alkynyloxy(sub-group H).

Preferred compounds of sub-group H are those in which

R₁ is C₁ -C₄ alkyl, C₁ -C₄ halogenoalkyl, vinyl, dimethylamino or C₅ -C₆cycloalkyl (sub-group Ha).

Compounds which are furthermore preferred within the scope of theformula I are those in which

R₃ is C₃ -C₄ alkyl (sub-group Hb).

A particularly preferred sub-group is formed by compounds within thescope of the formula I in which

R₁₀ is p-C₁ -C₄ alkoxy, p-C₃ -C₄ alkenyloxy or p-C₃ -C₄ alkynyloxy; and

R₁₁ is m-C₁ -C₄ alkoxy (sub-group Hc).

Important compounds of sub-group Hc are those in which

R₁ is C₁ -C₄ alkyl, vinyl or dimethylamino;

R₁₀ is p-methoxy, p-allyloxy or p-propargyloxy; and

R₁₁ is m-methoxy (sub-group Hca).

Particularly important compounds of sub-group Hca are those in which

R₁₀ is p-methoxy and

R₁₁ is m-methoxy (sub-group Hcb).

In the above formula I "halogen" includes fluorine, chlorine, bromineand iodine.

The alkyl, alkenyl and alkynyl radicals can be straight-chain orbranched, and this also applies to the alkyl, alkenyl, or alkynyl moietyof the halogenoalkyl, alkylsulfonylalkyl, alkenyloxy, alkynyloxy, alkoxyand alkylthio group and other groups.

Alkyl itself or as a constituent of another substituent is to beunderstood as meaning, for example, depending on the number of carbonatoms mentioned, methyl, ethyl, propyl, butyl, pentyl, dodecyl and theirisomers, for example isopropyl, isobutyl, tert-butyl or sec-butyl.Depending on the number of carbon atoms mentioned, cycloalkyl iscyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl orcyclooctyl.

A halogenoalkyl group can contain one or more (identical or different)halogen atoms, for example CHCl₂, CH₂ F, CCl₃, CH₂ Cl, CHF₂, CF₃, CH₂CH₂ Br, C₂ Cl₅, CH₂ Br, CHBrCl and the like.

The presence of at least one asymmetric carbon atom and/or at least oneasymmetric sulfur atom in the compounds of the formula I means that thecompounds can occur in optically isomeric forms. Geometric isomerism canalso occur due to the presence of an aliphatic --C═C-- double bond.Formula I is intended to include all these possible isomeric forms aswell as mixtures thereof.

Certain α-amino acid derivatives of a different type of structure havealready been proposed for controlling plant-injurious fungi (for examplein EP-398072, EP-425925, DE-4026966, EP-477639, EP-493683, DE-4035851,EP-487154, EP-496239, EP-550788 and EP-554729). However, the action ofthese preparations is not satisfactory. Surprisingly, novel microbicideshaving a high action have been found with the compound structure of theformula I.

DESCRIPTION OF PROCESS FOR THE PREPARATION OF COMPOUNDS ACCORDING TO THEINVENTION

The compounds of the formula I can be prepared

a) by reaction of a substituted amino acid of the formula II ##STR6## inwhich the radicals R₁, R₂ and R₃ and n are as defined above, orcarboxy-activated derivatives thereof, in the presence or absence of acatalyst, in the presence or absence of an acid-binding agent and in thepresence or absence of a diluent, with an amine of the formula III##STR7## in which R₄, R₅ and R₆ are as defined above.

The amino acid derivatives of the formula II required for carrying outprocess a) according to the invention are known per se or can beprepared by process aa) described below.

The amines of the formula III are generally known compounds of organicchemistry.

Carboxy-activated derivatives of the amino acid of the formula II areall the carboxy-activated derivatives, such as acid halides, for exampleacid chloride; and furthermore symmetric or mixed anhydrides, forexample the mixed O-alkyl-carboxylic acid anhydrides; and moreoveractivated esters, for example p-nitrophenyl esters orN-hydroxysuccinimide esters, as well as activated forms of the aminoacid which are produced in situ using condensation agents (for exampledicyclohexylcarbodiimide or carbonyldiimidazole).

The acid halides corresponding to the amino acid of the formula II canbe prepared by reacting the amino acid of the formula II with ahalogenating agent, for example phosphorus pentachloride, thionylchloride or oxalyl chloride, in a manner known per se.

The mixed anhydrides corresponding to the amino acid of the formula IIcan be prepared by reacting the amino acid of the formula II withchloroformic acid esters, for example chloroformic acid alkyl esters,preferably either butyl chloroformate, in the presence or absence of anacid-binding agent, such as an inorganic or organic base, for example atertiary amine, for example triethylamine, pyridine, N-methylpiperidineor N-methylmorpholine.

The reaction of the amino acid of the formula II or thecarboxy-activated derivatives of the amino acid of the formula II withan amine of the formula III takes place in an inert diluent. Examplesare: aromatic, non-aromatic or halogenated hydrocarbons, for examplechlorohydrocarbons, for example methylene chloride or toluene; ketones,for example acetone; esters, for example ethyl acetate; amides, forexample dimethylformamide; nitriles, for example acetonitrile, orethers, for example tetrahydrofuran, dioxane, diethyl ether ortert-butyl methyl ether; or water or mixtures of these inert diluents.The acid-binding agents which may be present are (in)organic bases, forexample an alkali metal or alkaline earth metal hydroxide or carbonate,for example sodium hydroxide, potassium hydroxide, sodium carbonate orpotassium carbonate, or, for example, a tertiary amine, for exampletriethylamine, pyridine, N-methylpiperidine or N-methylmorpholine. Thetemperatures are -80° to +150° C., preferably -20° to +60° C.

Compounds of the formula I can also be prepared

b) by reaction of a sulfonic acid derivative or sulfinic acid derivativeof the formula IV ##STR8## in which R₁ and n are as defined above and inwhich X is halogen (chlorine or bromine), the radical R₁ --SO₂ --O-- orthe radical R₁ --SO--O--, with an amine of the formula V ##STR9## inwhich R₂, R₃, R₄, R₅ and R₆ are as defined above.

The sufonic acid derivatives or sulfinic acid derivatives of the formulaIV required for process b) are known per se. The amines of the formula Vwhich are likewise required are similarly known per se or can beprepared by processes bb) described below.

The reaction of the sulfonic acid derivatives or sulfinic acidderivatives of the formula IV with an amine of the formula V takes placein an inert diluent. Examples are: aromatic, non-aromatic or halogenatedhydrocarbons, for example chlorohydrocarbons, for example methylenechloride or toluene; ketones, for example acetone; esters, for exampleethyl acetate; amides, for example dimethylformamide; nitriles, forexample acetonitrile, or ethers, for example tetrahydrofuran, dioxane,diethyl ether or tert-butyl methyl ether; or water or mixtures of theseinert diluents. Acid-binding agents which may be present are (in)organicbases, for example an alkali metal or alkaline earth metal hydroxide orcarbonate, for example sodium hydroxide, potassium hydroxide, sodiumcarbonate or potassium carbonate, or, for example, a tertiary amine, forexample triethylamine, pyridine, N-methylpiperidine orN-methylmorpholine. The temperatures are -80° to +150° C., preferably-20° to +60° C.

Compounds of the formula I can also be prepared

c) by oxidation of a compound of the formula I' ##STR10## with anoxidizing agent, in which R₁, R₂, R₃, R₄, R₅ and R₆ are as definedabove, with the proviso that none of the substituents R₁, R₂, R₃, R₅ orR₆ comprises a thiol or alkylthio group.

Oxidizing agents are either organic oxidizing agents, such as alkylhydroperoxides, for example cumyl hydroperoxide, or inorganic oxidizingagents, such as peroxides, for example hydrogen peroxide, or such astransition metal oxides, for example chromium trioxide, and transitionmetal oxide salts, for example potassium permanganate, potassiumdichromate or sodium dichromate.

The reaction of the compounds of the formula I' with the oxidizing agenttakes place in an inert solvent, for example water or a ketone, forexample acetone, or in mixtures thereof, in the presence or absence ofan acid or in the presence or absence of a base, at temperatures of -80°to +150° C.

aa) The amino acid derivatives of the formula II required can beprepared by reaction of an amino acid of the formula VI ##STR11## inwhich R₂ and R₃ are as defined above, with a sulfonic acid derivative orsulfinic acid derivative of the formula IV ##STR12## in which R₁ and nare as defined above and in which X is halogen (chlorine or bromine),the radical R₁ --SO₂ --O-- or the radical R₁ --SO--O--.

The sulfonic acid derivatives or sulfinic acid derivatives of theformula IV required for process aa) and the amino acids of the formulaVI are known.

The solvents (or diluents), acid-binding agents and temperature rangecorrespond to the statements for reaction a) or b).

bb) The amines of the formula V required can be prepared by acidhydrolysis of a compound of the formula VII ##STR13##

Compounds of the formula VII have been disclosed in the literature, forexample in EP-398072, DE-4026966, EP-493683, EP-496239, EP-550788 andEP-554728.

The reaction of the compounds of the formula VII with an inorganic ororganic acid, for example mineral acids (hydrogen halide acid orsulfuric acid) or carboxylic acids, for example acetic acid ortrifluoroacetic acid, or sulfonic acids, for example methanesulfonicacid or p-toluenesulfonic acid, can be carried out in an inert diluent(hydrocarbons, for example methylene chloride or toluene; ketones, forexample acetone; or water) at temperature of -40° to +150° C. Ifappropriate, mixtures of different acids and different diluents can alsobe employed. The acid itself is also capable of serving as the diluent.

The compounds of the formula I are oils or solids which are stable atroom temperature and have valuable microbicidal properties. They can beemployed preventively and curatively in the agricultural sector or inrelated areas for controlling plant-injurious microorganisms. The activeingredients of the formula I according to the invention not only have anoutstanding microbicidal, in particular fungicidal, action, coupled withlow use concentrations, but also are particularly well tolerated byplants.

Surprisingly, it has now been found that compounds of the formula I havea very favourable biocidal spectrum for practical requirements forcontrolling phytopathogenic microorganisms, in particular fungi. Theyhave very advantageous curative and preventive properties and areemployed for the protection of numerous crop plants. Using the activeingredients of the formula I, the pests occurring on plants or parts ofplants (fruit, blossom, foliage, stems, tubers, roots) of differentcrops of useful plants can be checked or destroyed, parts of plantswhich grow on later, for example, also remaining protected fromphytopathogenic fungi.

The novel active ingredients of the formula I prove to be preferentiallyactive against specific genera of the fungal class of Fungi imperfecti(for example Cercospora, Botrytis, Helminthosporium, Fusarium Septoria,Pyricularia and Alternaria), Basidiomycetes (for example the generaHemileia, Rhizoctonia and Puccinia) and Ascomycetes (for examplePodosphaera, Monilinia, Uncinula, Cercosporella, Erysiphe and Venturia),Deuteromycetes (for example Rhynchosporium), and in particular againstOomycetes (for example Plasmopara, Peronospora, Pythium, Bremia andPhytophthora). They are therefore a valuable enrichment of compositionsin crop protection for controlling phytopathogenic fungi. The compoundsof the formula I furthermore can be employed as dressing agents for thetreatment of seed (fruit, tubers, grains) and plant seedlings forprotection against fungal infections and against phytopathogenic fungiwhich occur in the soil.

The invention also relates to compositions which comprise compounds ofthe formula I as active ingredient components, in particular cropprotection compositions, and to their use in the agricultural sector orrelated areas.

The invention moreover also relates to the preparation of thesecompositions, which comprises intimate mixing of the active substancewith one or more substances or substance groups described herein. Theprocess for treatment of plants which comprises application of the novelcompounds of the formula I or of the novel compositions is alsoincluded.

Target crops for the crop protection use disclosed herein are, in thecontext of this invention, for example, the following plant species:cereals (wheat, barley, rye, oats, rice, maize, sorghum, dinkel,triticale and related species); beet (sugar and feed beet); pome, stoneand soft fruit (apples, pears, plums, peaches, almonds, cherries,strawberries, raspberries and blackberries); pulses (beans, lentils,peas, soya); oil crops (rape, mustard, poppy, olive, sunflower, coconut,castor, cacao, groundnut); cucumber plants (pumpkins, cucumbers,melons); fibre plants (cotton, flax, hemp, jute); citrus fruits(oranges, lemons, grapefruits, mandarines); types of vegetables(spinach, lettuce, asparagus, cabbage species, carrots, onions,tomatoes, potatoes, paprika); bay plants (avocado, cinnamonium, camphor)or plants such as tobacco, nuts, coffee, sugarcane, tea, pepper, vines,hops, banana and natural rubber plants and ornamentals.

Active ingredients of the formula I are usually used in the form ofcompositions and can be introduced onto the area or plant to be treatedat the same time as or successively with other active ingredients. Theseother active ingredients can be either fertilizers, mediators of traceelements or other preparations which influence plant growth. It is alsopossible to use here selective herbicides as well as insecticides,fungicides, bactericides, nematicides, molluscicides or mixtures ofseveral of these preparations, if appropriate together with othercarriers, surfactants or other application-promoting additives customaryin formulation technology.

Suitable carriers and additives can be solid or liquid and correspond tothe substances used for this purpose in formulation technology, forexample naturally occurring or regenerated mineral substances, solvents,dispersants, wetting agents, tackifiers, thickeners, binders orfertilizers.

A preferred method of application of an active ingredient of the formulaI or of an agrochemical composition which comprises at least one ofthese active ingredients is application to the foliage (leafapplication). The application frequency and rate of application dependon the danger of infestation by the pathogen in question. The compoundsof the formula I can also be applied to plant propagation material(dressing of grains, fruit, tubers, shoots, seedlings, roots and thelike), for example either by impregnating cereal grains (seed) or potatotubers or freshly cut shoots in a liquid composition of the activeingredient or coating them with a solid composition.

The compounds of the formula I are employed here in unchanged form or,preferably, together with the auxiliaries customary in formulationtechnology. For this purpose, they are expediently processed, forexample, to emulsion concentrates, brushable pastes, directly sprayableor dilutable solutions, dilute emulsions, wettable powders, solublepowders, dusts or granules, by encapsulation in, for example, polymericsubstances in a known manner. The methods of use, such as spraying,atomizing, dusting, scattering, brushing on or pouring, like the natureof the composition, are chosen according to the intended aims and thegiven circumstances.

Favourable rates of application are in general 5 g to 2 kg of activesubstance (AS) per hectare (ha), preferably 10 g to 1 kg of AS/ha, inparticular 20 g to 600 g of AS/ha.

The formulations, i.e. the preparations, formulations or compositionscomprising the active ingredient of the formula I and, if appropriate, asolid or liquid additive, are prepared in a known manner, for example byintimate mixing and/or grinding of the active ingredient with extenders,such as solvents, solid carriers and if appropriate surface-activecompounds (surfactants).

Solvents are: aromatic hydrocarbons, preferably C₈ to C₁₂ fractions,such as xylene mixtures or substituted naphthalenes, phthalic acidesters, such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons,such as cyclohexane or paraffins, alcohols and glycols and ethers andesters thereof, such as ethanol, ethylene glycol or ethylene glycolmonomethyl or monoethyl ether, ketones, such as cyclohexanone, stronglypolar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide ordimethylformamide, and plant oils, which may be epoxidized, such asepoxidized coconut oil or soya oil, and water.

Solid carriers, for example for dusts and dispersible powders, are as arule natural rock powders, such as calcite, talc, kaolin,montmorillonite or attapulgite. Highly disperse silicic acid or highlydisperse absorbent polymers can also be added to improve the physicalproperties. Granular absorptive granule carriers are porous types, suchas pummice, broken brick, sepiolite or bentonite, and non-sorptivecarrier materials are, for example, calcite or sand. A large number ofpregranulated materials of inorganic nature, such as dolomite orcomminuted plant residues, can also be used.

Surface-active compounds are, depending on the nature of the activeingredient of the formula I to be formulated, nonionic, cationic and/oranionic surfactants with good emulsifying, dispersing and wettingproperties. Surfactants are also to be understood as meaning surfactantmixtures.

Suitable anionic surfactants can be either so-called water-solublesoaps, or water-soluble synthetic surface-active compounds.

Examples of nonionic surfactants are nonylphenolpolyethoxyethanols,castor oil polyglycol ether, polypropylene/polyethylene oxide adducts,tributylphenoxypolyethylene-ethanol, polyethylene glycol andoctylphenoxypolyethoxyethanol.

Fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylenesorbitan trioleate, can also be used.

The cationic surfactants are, in particular, quaternary ammonium saltswhich contain at least one alkyl radical having 8 to 22 C atoms as Nsubstituents and lower, non-halogenated or halogenated alkyl, benzyl orlower hydroxyalkyl radicals as further substituents.

Other surfactants which are customary in formulation technology areknown to the expert or can be found from the relevant technicalliterature.

The agrochemical preparations as a rule comprise 0.1 to 99 percent byweight, in particular 0.1 to 95 percent by weight, of active compound ofthe formula I, 99.9 to 1 percent by weight, in particular 99.8 to 5percent by weight, of a solid or liquid additive and 0 to 25 percent byweight, in particular 0.1 to 25 percent by weight, of a surfactant.

While concentrated compositions tend to be preferred as commercialproducts, the end user as a rule uses dilute compositions.

The compositions can also comprise further additives, such asstabilizers, defoamers, viscosity regulators, binders or tackifiers, aswell as fertilizers, trace element mediators or other preparations whichinfluence plant growth, in order to achieve special effects.

The following examples illustrate the invention described above withoutlimiting it in its scope in any manner. Temperatures are stated indegrees Celsius.

PREPARATION EXAMPLES FOR THE COMPOUNDS OF THE FORMULA I

H-1.1.: (R,S)-2-(N,N-dimethylsulfamoyl)-amino-3-methyl-butyric acidN-(1,1-diphenylmethyl)-amide [Process a)] ##STR14##

2.2 g of (R,S)-2-(N,N-dimethylsulfamoyl)-amino-3-methyl-butyric acid and1.1 ml of N-methylmorpholine are cooled to -10° C. in 50 ml oftetrahydrofuran, while stirring. 1.25 ml of isobutyl chloroformate areadded dropwise and the reaction mixture is subsequently stirred at -10°C. for 30 minutes. 1.7 ml of 1-amino-1,1-diphenylmethane are now addedand the mixture is stirred at room temperature for 6 hours. The reactionmixture is introduced into 200 ml of 2N hydrochloric acid and extractedtwice with 200 ml of ethyl acetate each time. The organic phases arewashed once with 200 ml of 2N hydrochloric acid, once with 100 ml ofsaturated sodium chloride solution, twice with 200 m l of 2N potassiumbicarbonate solution each time and once with 100 ml of saturated sodiumchloride solution, dried over magnesium sulfate and concentrated.(R,S)-2-(N,N-dimethylsulfamoyl)-amino-3-methyl butyric acidN-(1,1-diphenylmethyl)-amide, which can be purified by recrystallizationfrom ethyl acetate/hexane, is obtained, melting point 156°-158° C.

The compounds shown in Table 1 are obtained analogously to this example.

                                      TABLE 1                                     __________________________________________________________________________    (prepared according to process a))                                             ##STR15##                                   (I)                                                                         Physical                           Comp.                                      data                               No. R.sub.1  n R.sub.2                                                                          R.sub.3   R.sub.4                                                                         R.sub.5                                                                            R.sub.6 m.p. °C.                    __________________________________________________________________________    1.1 Me.sub.2 N                                                                             1 H  2-propyl  H Phenyl                                                                             Phenyl  156-158                            1.2 Me.sub.2 N                                                                             1 H  2-propyl  H H    3,4-D   Oil                                1.3 Methyl   0 H  2-propyl  H H    3,4-D                                      1.4 2-Propyl 0 H  2-propyl  H H    3,4-D                                      1.5 2-Methyl-2-propyl                                                                      0 H  2-propyl  H H    3,4-D                                      1.6 Methyl   0 H  2-propyl  H H    3,4-D                                      1.7 2-Propyl 0 H  2-propyl  H H    3,4-D                                      1.8 2-Methyl-2-propyl                                                                      0 H  2-propyl  H H    3,4-D                                      1.9 Me.sub.2 N                                                                             1 H  Methyl    H H    3,4-D                                      1.10                                                                              Methyl   1 H  Methyl    H H    3,4-D                                      1.11                                                                              Me.sub.2 N                                                                             1 H  Ethyl     H H    3,4-D   108-111                            1.12                                                                              Methyl   1 H  Ethyl     H H    3,4-D                                      1.13                                                                              Me.sub.2 N                                                                             1 H  Cyclopropyl                                                                             H H    3,4-D                                      1.14                                                                              Methyl   1 H  Cyclopropyl                                                                             H H    3,4-D                                      1.15                                                                              Me.sub.2 N                                                                             1 H  Cyclopropylmethyl                                                                       H H    3,4-D                                      1.16                                                                              Methyl   1 H  Cyclopropylmethyl                                                                       H H    3,4-D                                      1.17                                                                              Me.sub.2 N                                                                             1 Me 2-Propyl  H H    3,4-D                                      1.18                                                                              Methyl   1 Me 2-Propyl  H H    3,4-D                                      1.19                                                                              Me.sub.2 N                                                                             1 Me Methyl    H H    3,4-D                                      1.20                                                                              Methyl   1 Me Methyl    H H    3,4-D   134-135                            1.21                                                                              Me.sub.2 N                                                                             1 Tetramethylene                                                                             H H    3,4-D                                      1.22                                                                              Methyl   1 Tetramethylene                                                                             H H    3,4-D   152-154                            1.23                                                                              Me.sub.2 N                                                                             1 H  1-(2-Methyl-2-                                                                          H H    3,4-D                                                        propoxy)-ethyl                                              1.24                                                                              Methyl   1 H  1-(2-Methyl-2-                                                                          H H    3,4-D                                                        propoxy)-ethyl                                              1.25                                                                              Ethyl    1 H  Ethyl     H (S)Me                                                                              Phenyl  122-123                            1.26                                                                              Ethyl    1 H  Ethyl     H H    3,4-D   107-109                            1.27                                                                              Ethyl    1 H  Ethyl     H (R)Me                                                                              Phenyl  122-123                            1.28                                                                              Ethyl    1 H  Ethyl     H Phenyl                                                                             Phenyl  151-153                            1.29                                                                              Ethyl    1 H  1-(2-Methyl-2-                                                                          H H    3,4-D   Oil                                                  propoxy)-ethyl                                              1.30                                                                              Ethyl    1 H  1-(2-Methyl-2-                                                                          H (R)Me                                                                              Phenyl  84-86                                                propoxy)-ethyl                                              1.31                                                                              Ethyl    1 H  1-(2-Methyl-2-                                                                          H (S)Me                                                                              Phenyl  138-139                                              propoxy)-ethyl                                              1.32                                                                              Ethyl    1 H  1-(2-Methyl-2-                                                                          H Phenyl                                                                             Phenyl  115-116                                              propoxy)-ethyl                                              1.33                                                                              Ethyl    1 H  2-Propyl  H Methyl                                                                             4-Cl-phenyl                                                                           152-154                            1.34                                                                              Ethyl    1 H  2-Propyl  H H    3,4,5-T Resin                              1.35                                                                              Ethyl    1 H  2-Propyl  H H    3-MeO-benzyl                                                                          97-99                              1.36                                                                              Ethyl    1 H  2-Propyl  H (S)Me                                                                              Phenyl  177-178                            1.37                                                                              Ethyl    1 H  2-Propyl  H Phenyl                                                                             Phenyl  188-189                            1.38                                                                              Ethyl    1 H  2-Propyl  H (R)Me                                                                              Phenyl  177-178                            1.39                                                                              Ethyl    1 H  2-Propyl  H H    2,3-D   95-96                              1.40                                                                              Ethyl    1 H  2-Propyl  H H    4-MeO-benzyl                                                                          106-107                            1.41                                                                              Ethyl    1 H  2-Propyl  H H    3,5-D   85-87                              1.42                                                                              Ethyl    1 H  2-Propyl  H H    2,5-D   85-87                              1.43                                                                              Methyl   1 Tetramethylene                                                                             H Phenyl                                                                             Phenyl  242-243                            1.44                                                                              Methyl   1 H  Ethyl     H (R)Me                                                                              Phenyl  116-117                            1.45                                                                              Methyl   1 H  Ethyl     H (S)Me                                                                              Phenyl  115-117                            1.46                                                                              Methyl   1 Me Methyl    H Methyl                                                                             Phenyl  120-121                            1.47                                                                              Methyl   1 Me Methyl    H Phenyl                                                                             Phenyl  173-174                            1.48                                                                              Methyl   1 Tetramethylene                                                                             H Methyl                                                                             Phenyl  163-165                            1.40                                                                              Methyl   1 H  Ethyl     H Phenyl                                                                             Phenyl  190-192                            1.50                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H (R)Me                                                                              Phenyl  114-115                            1.51                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H (S)Me                                                                              Phenyl  108-109                            1.52                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H Methyl                                                                             4-Cl-phenyl                                                                           112-113                            1.53                                                                              Me.sub.2 N                                                                             1 H  2-Butyl   H H    4-MeO-benzyl                                                                          85-87                              1.54                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H Methyl                                                                             4-MeO-benzyl                                                                          93-96                              1.55                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H (S)Me                                                                              4-Me-phenyl                                                                           161-163                            1.56                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H (R)Me                                                                              4-Me-phenyl                                                                           166-168                            1.57                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H H    4-MeO-benzyl                                                                          82-83                              1.58                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H H    3-MeO-benzyl                                                                          Resin                              1.59                                                                              Me.sub.2 N                                                                             1 H  2-Butyl   H H    3-MeO-benzyl                                                                          Resin                              1.60                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H Methyl                                                                             4-Fluorphenyl                                                                         111-112                            1.61                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H H    3,5-D   Oil                                1.62                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H H    2,5-D   87-89                              1.63                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H H    2,3-D   90-91                              1.64                                                                              Ethyl    1 H  2-Propyl  H H    3-MeO-4-PrO-                                                                          Resin                                                                 benzyl                                     1.65                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H Methyl                                                                             3,4-D   105-147                            1.66                                                                              Ethyl    1 H  2-Propyl  H H    4-MeO-3-PrO-                                                                          101-103                                                               benzyl                                     1.67                                                                              Ethyl    1 H  2-Propyl  H H    3-MeO-4-                                                                              112-114                                                               AllylO-benzyl                              1.68                                                                              Ethyl    1 H  2-Propyl  H H    4-MeO-3-                                                                              Resin                                                                 AllylO-benzyl                              1.69                                                                              Ethyl    1 H  2-Propyl  H H    3-EtO-4-MeO-                                                                          89-91                                                                 benzyl                                     1.70                                                                              Ethyl    1 H  2-Propyl  H H    3-MeO-4-                                                                              109-110                                                               PropargylO-                                                                   benzyl                                     1.71                                                                              Me.sub.2 N                                                                             1 H  2-Butyl   H H    3-MeO-4-                                                                              Resin                                                                 PropargylO-                                                                   benzyl                                     1.72                                                                              Me.sub.2 N                                                                             1 H  2-Butyl   H H    4-MeO-3-PrO-                                                                          Resin                                                                 benzyl                                     1.73                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H H    4-MeO-3-Me-                                                                           Resin                                                                 benzyl                                     1.74                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H H    3-MeO-4-                                                                              Resin                                                                 PropargylO-                                                                   benzyl                                     1.75                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H H    4-MeO-3-PrO-                                                                          84-85                                                                 benzyl                                     1.76                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H H    3-MeO-4-                                                                              Resin                                                                 AllylO-benzyl                              1.77                                                                              Me.sub.2 N                                                                             1 H  2-Butyl   H H    3-EtO-4-MeO-                                                                          85-88                                                                 benzyl                                     1.78                                                                              Me.sub.2 N                                                                             1 H  2-Butyl   H H    3-MeO-4-                                                                              Resin                                                                 AllylO-benzyl                              1.79                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H H    3-EtO-4-MeO-                                                                          87-89                                                                 benzyl                                     1.80                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H Methyl                                                                             4-Ethylphenyl                                                                         Resin                              1.81                                                                              Ethyl    1 H  2-Propyl  H H    4-MeO-3-Me-                                                                           89-91                                                                 benzyl                                     1.82                                                                              Ethyl    1 H  2-Propyl  H H    4-EtO-3-MeO-                                                                          87-89                                                                 benzyl                                     1.83                                                                              Me.sub.2 N                                                                             1 H  2-Propyl  H H    4-EtO-3-MeO-                                                                          84-86                                                                 benzyl                                     1.84                                                                              Ethyl    1 H  2-Propyl  H Methyl                                                                             3,4-D   112-160                            1.85                                                                              Ethyl    1 H  2-Propyl  H H    1-(3,4-Di-MeO-                                                                        114-130                                                               phenyl)-ethyl                              __________________________________________________________________________     2,3-D = 2,3dimethoxy-benzyl, 2,5D = 2,5dimethoxy-benzyl,                      3,4D = 3,4dimethoxy-benzyl, 3,5D = 3,5dimethoxy-benzyl,                       3,4,5T = 3,4,5trimethoxy-benzyl                                               Stereochemistry on the α C atom of the amino acid (where known):        R, S for compounds 1.1 to 1.5, 1.9, 1.10, 1.13 to 1.18                        S for compounds 1.6 to 1.8, 1.11, 1.12, 1.23 to 1.42, 1.44, 1.45, 1.49 to     1.83                                                                     

H-2.1: (R,S)-methanesulfonic acidN-[2-methyl-1-(N-benzyl)-carbamoyl]-propyl-amide [Process a)] ##STR16##

3.9 g of (R,S)-methanesulfonic acid N-(2-methyl-1-carboxy)-propyl-amideand 2.2 ml of N-methylmorpholine are cooled to -20° C. in 100 ml oftetrahydrofuran, while stirring. 2.5 ml of isobutyl chloroformate areadded dropwise to this mixture in the course of 5 minutes. The mixtureis then subsequently stirred for 30 minutes, the reaction temperatureincreasing to -10° C. The mixture is then cooled again to -20° C. and2.2 ml of benzylamine are added dropwise over the course of 5 minutes.The reaction mixture is allowed to warm to room temperature and isstirred for a further 4 hours. It is then introduced in 200 ml of water.The mixture is extracted twice with 400 ml of ethyl acetate each time.The organic phases are washed once with 200 ml of saturated sodiumchloride solution, combined, dried over sodium sulfate and concentrated.(R,S)-methanesulfonic acidN-[2-methyl-1-(N-benzyl)-carbamoyl]-propyl-amide, which can be purifiedby recrystallization from ethyl acetate/hexane, is obtained, meltingpoint 115°-116° C.

The compounds shown in Table 2 are obtained analogously to this example.

                  TABLE 2                                                         ______________________________________                                        (prepared according to process a))                                             ##STR17##                                                                    Comp.                                                                         No.   R.sub.4  R.sub.5  R.sub.6     Physical data                             ______________________________________                                        2.1   H        H        Phenyl      m.p.                                                                          115-116° C.                        2.2   H        Methyl   Phenyl      m.p.                                                                          132-134° C.                        2.3   Methyl   Methyl   Phenyl                                                2.4   H        H        m-Trifluoromethyl-                                                                        m.p.                                                              phenyl      154-155° C.                        2.5   H        Methyl   P-Fluorophenyl                                                                            m.p.                                                                          106-109° C.                        2.6   H        Methyl   p-Chlorophenyl                                                                            m.p.                                                                          150-156° C.                        2.7   H        Methyl   p-Methoxyphenyl                                       2.8   H        Methyl   m-Methoxyphenyl                                       2.9   H        Methyl   m-Trifluoromethyl                                     2.10  H        Methyl   Benzyl                                                2.11  H        Methyl   p-Chlorobenzyl                                        2.12  H        Methyl   2,5-Dimethoxy-4-                                                              methylbenzyl                                          2.13  Methyl   Methyl   Benzyl                                                2.14  Methyl   Methyl   p-Fluorobenzyl                                        2.15  Methyl   Methyl   p-Chlorobenzyl                                        2.17  H        Phenyl   Phenyl      m.p.                                                                          190-191° C.                        2.18  H        Phenyl   p-Chlorophenyl                                        2.19  H        Phenyl   p-Methoxyphenyl                                       2.20  H        Phenyl   p-Methylphenyl                                        2.21  H        Phenyl   3,5-di-Trifluoro-                                                             methylphenyl                                          2.22  H        H        1-Phenylethyl                                         2.23  H        H        1-(4-Chlorophenyl)-                                                           ethyl                                                 2.24  H        H        2-(4-Chlorophenyl)-                                                           propyl                                                2.25  H        H        Phenyl                                                2.26  H        Methyl   Phenyl                                                2.27  Methyl   Methyl   Phenyl                                                2.28  H        H        m-Trifluoromethyl-                                                            phenyl                                                2.29  H        Methyl   p-Fluorophenyl                                        2.30  H        Methyl   p-Chlorophenyl                                                                            m.p.                                                                          139-142° C.                        2.31  H        Methyl   p-Methoxyphenyl                                       2.32  H        Methyl   m-Methoxyphenyl                                       2.33  H        Methyl   m-Trifluoromethyl                                     2.34  H        Methyl   Benzyl                                                2.35  H        Methyl   p-Chlorobenzyl                                        2.36  H        Methyl   2,5-Dimethoxy-4-                                                              methylbenzyl                                          2.37  Methyl   Methyl   Benzyl                                                2.38  Methyl   Methyl   p-Fluorobenzyl                                        2.39  Methyl   Methyl   p-Chlorobenzyl                                        2.40  H        Phenyl   Phenyl      m.p.                                                                          191-193° C.                        2.41  H        Phenyl   p-Chlorophenyl                                        2.42  H        Phenyl   p-Methoxyphenyl                                       2.43  H        Phenyl   p-Methylphenyl                                        2.44  H        Phenyl   3,5-di-Trifluoro-                                                             methylphenyl                                          2.45  H        H        1-Phenylethyl                                         2.46  H        H        1-(4-Chlorophenyl)-                                                           ethyl                                                 2.47  H        H        2-(4-Chlorophenyl)-                                                           propyl                                                2.48  H        H        p-Nitrophenyl                                                                             m.p.                                                                          167-168° C.                        2.49  H        H        o-Trifluoromethyl-                                                                        m.p.                                                              phenyl      168-169° C.                        2.50  H        (R)Me    Phenyl      m.p.                                                                          139-142° C.                        2.51  H        (S)Me    Phenyl      m.p.                                                                          138-139° C.                        ______________________________________                                         Stereochemistry disclosed on the α C atom of the amino acid:            R, S for compounds 2.1 to 2.24, 2.48                                          S for compounds 2.25 to 2.47, 2.49 to 2.51                               

H-3.1: (S)-2-(N,N-dimethylsulfamoyl)-amino-3-methyl-butyric acidN-[2-(3,4-dimethoxy-phenyl)-ethyl]-amide [Process b)] ##STR18##

7.2 g of (S)-2-amino-3-methyl-butyric acidN-[2-(3,4-dimethoxyphenyl)-ethyl]-amide and 4 ml of triethylamine areinitially introduced in 120 ml of 1,4-dioxane at room temperature, whilestirring. 2.8 ml of N,N-dimethylsulfamoyl chloride are added dropwise inthe course of 5 minutes. The reaction mixture is then stirred at roomtemperature for 20 hours and subsequently introduced into 80 ml of 2Nhydrochloric acid. The mixture is extracted twice with 200 ml of ethylacetate each time. The organic phases are washed once with 80 ml of 2Nhydrochloric acid, once with 80 ml of saturated sodium chloridesolution, once with 80 ml of 5% sodium bicarbonate solution and oncewith 80 ml of saturated sodium chloride solution, combined, dried oversodium sulfate and concentrated.(S)-2-(N,N-dimethylsulfamoyl)-amino-3-methyl-butyric acidN-[2-(3,4-dimethoxyphenyl)-ethyl]-amide, which can be purified byrecrystallization from ethyl acetate/hexane, is obtained, melting point97°-99° C.

The compounds shown in Table 3 and Table 3a are obtained analogously tothis example.

                  TABLE 3                                                         ______________________________________                                        (prepared according to process b))                                             ##STR19##                                                                    Comp.                                                                         No.   R.sub.1         R.sub.3   Physical data                                 ______________________________________                                        3.1   NMe.sub.2       2-Propyl  m.p. 97-99° C.                         3.2   NMe.sub.2       2-Butyl   m.p. 91-92° C.                         3.3   NMe.sub.2       2-Methyl- Resin                                                               propyl                                                  3.4   NMe.sub.2       2-MeS-    Resin                                                               ethyl                                                   3.5   NMe.sub.2       Hydroxy-                                                                      methyl                                                  3.6   NMe.sub.2       1-Hydroxy-                                                                              Resin                                                               ethyl                                                   3.7   NMeEt           2-Propyl  m.p. 76-78° C.                         3.8   NMeEt           2-Butyl                                                 3.9   NEt.sub.2       2-Propyl  m.p. 95-96° C.                         3.10  NEt.sub.2       2-Butyl   m.p. 63-69° C.                         3.11                                                                                 ##STR20##      2-Propyl  m.p. 76-77° C.                         3.12                                                                                 ##STR21##      2-Butyl                                                 3.13  Methyl          2-Propyl  m.p. 130-132° C.                       3.14  Methyl          2-Butyl   m.p. 147-148° C.                       3.15  Methyl          2-Methyl- Resin                                                               propyl                                                  3.16  Methyl          2-MeS-    m.p. 126-127° C.                                             ethyl                                                   3.17  Methyl          Hydroxy-                                                                      methyl                                                  3.18  Methyl          1-Hydroxy-                                                                              m.p. 140-141° C.                                             ethyl                                                   3.19  Ethyl           2-Propyl  m.p. 148-152° C.                       3.20  Ethyl           2-Butyl   m.p. 137-138° C.                       3.21  Ethyl           2-Methyl- Resin                                                               propyl                                                  3.22  Ethyl           2-MeS-    m.p. 79-81° C.                                               ethyl                                                   3.23  Ethyl           Hydroxy-                                                                      methyl                                                  3.24  Ethyl           1-Hydroxy-                                                                              m.p. 82-83° C.                                               ethyl                                                   3.25  Propyl          2-Propyl  m.p. 108-109° C.                       3.26  Propyl          2-Butyl   m.p. 95-96° C.                         3.27  2-Propyl        2-Propyl                                                3.28  2-Propyl        2-Butyl                                                 3.29  Butyl           2-Propyl  m.p. 81-84° C.                         3.30  Butyl           2-Butyl   m.p. 105-106° C.                       3.31  2-Butyl         2-Propyl                                                3.32  2-Butyl         2-Butyl                                                 3.33  2-Methyl-propyl 2-Propyl                                                3.34  2-Methyl-propyl 2-Butyl                                                 3.35  2-Methyl-2-propyl                                                                             2-Propyl                                                3.36  2-Methyl-2-propyl                                                                             2-Butyl                                                 3.37  Pentyl          2-Propyl                                                3.38  Hexyl           2-Propyl                                                3.39  Octyl           2-Propyl  m.p. 77-78° C.                         3.40  Decyl           2-Propyl  m.p. 106-107° C.                       3.41  Dodecyl         2-Propyl                                                3.42  Vinyl           2-Propyl  m.p. 136-137° C.                       3.43  Vinyl           2-Butyl   m.p. 149-150° C.                       3.44  Vinyl           2-Methyl- Resin                                                               propyl                                                  3.45  Vinyl           2-MeS-    m.p. 129-130° C.                                             ethyl                                                   3.46  Vinyl           Hydroxy-                                                                      methyl                                                  3.47  Vinyl           1-Hydroxy-                                                                              m.p. 134-135° C.                                             ethyl                                                   3.48  Trifluoromethyl 2-Propyl  m.p. 120-121° C.                       3.49  Trifluoromethyl 2-Butyl                                                 3.50  Chloromethyl    2-Propyl  m.p. 131-132° C.                       3.51  Chloromethyl    2-Butyl                                                 3.52  Dichloromethyl  2-Propyl                                                3.53  Dichloromethyl  2-Butyl                                                 3.54  Trichloromethyl 2-Propyl                                                3.55  Trichloromethyl 2-Butyl                                                 3.56  2,2,2-Trifluoromethyl                                                                         2-Propyl                                                3.57  2,2,2-Trifluoromethyl                                                                         2-Butyl                                                 3.58  3-Chloropropyl  2-Propyl  m.p. 117-118° C.                       3.59  3-Chloropropyl  2-Butyl                                                 3.60  2-Methoxy-ethyl 2-Propyl                                                3.61  2-Methoxy-ethyl 2-Butyl                                                 3.62  2-Methanesulfonyl-ethyl                                                                       2-Propyl                                                3.63  2-Methanesulfonyl-ethyl                                                                       2-Butyl                                                 3.64  Methylsulfonyl-methyl                                                                         2-Propyl  m.p. 136-137° C.                       3.65  2,2,2-Trifluoroethyl                                                                          2-Propyl  m.p. 143-144° C.                       3.66  NH.sub.2        2-Propyl  m.p. 136-137° C.                       3.67  NH.sub.2        2-Butyl   m.p. 137-138° C.                       3.68  NH(CH.sub.3)    2-Propyl  m.p. 133-136° C.                       3.69  NH(CH.sub.3)    2-Butyl   m.p. 142-144° C.                       3.70  NH(Ethyl)       2-Propyl  m.p. 105-106° C.                       3.71  NH(Ethyl)       2-Butyl   m.p. 104-105° C.                       ______________________________________                                         Stereochemistry on the α C atom of the amino acid: S               

                  TABLE 3a                                                        ______________________________________                                        (prepared according to process b))                                             ##STR22##                                                                    Comp.                                                                         No.    R.sub.1         R.sub.3  Physical data                                 ______________________________________                                        3.90   2-Propyl        2-Propyl Resin                                         3.91   2-Butyl         2-Propyl Resin                                         3.92   2-Butyl         2-Butyl  Resin                                         3.93   2-Methyl-propyl 2-Propyl m.p. 113-114° C.                       3.94   2-Methyl-propyl 2-Butyl  m.p. 102-103° C.                       3.95   Pentyl          2-Propyl m.p. 91-92° C.                         3.96   Pentyl          2-Butyl  m.p. 74-75° C.                         3.97   Hexyl           2-Propyl m.p. 94-95° C.                         3.98   Hexyl           2-Butyl  m.p. 99-100° C.                        3.99   Cyclohexyl      2-Propyl Resin                                         3.100  Cyclopentyl     2-Propyl Resin                                         3.101  Cyclopentyl     2-Butyl  Resin                                         3.102  Cyclohexyl      2-Butyl  Resin                                         3.103  2-(MeO-carbonyl)-ethyl                                                                        2-Propyl m.p. 121-123° C.                       ______________________________________                                         Stereochemistry on the α C atom of the amino acid: S               

H-6.1: (S)-2(isopropylsulfonyl)-amino-3-methyl-butyricacid-N-[2-(3,4-dimethoxyphenyl)-ethyl]-amide [Process c)] ##STR23##

3.7 g of (S)-2-(isopropylsulfinyl)-amino-3-methyl-butyric acidN-[2-(3,4-dimethoxyphenyl)-ethyl]-amide (Example 3.90) are dissolved in50 ml of acetone at room temperature. An acetone solution saturated withpotassium permanganate is added dropwise to this stirred solution untilthe reaction mixture retains the violet colour of the permanganate; thereaction mixture is then stirred at room temperature for 45 minutes. Theresulting manganese dioxide is removed by filtration over Celite. Thefiltrate is evaporated to dryness and the resulting residue is dissolvedin 500 ml of methyl acetate. This organic phase is washed once with 200ml of water, dried over sodium sulfate and concentrated. The resultingresidue is chromatographed over silica gel with a mixture of one part ofmethyl acetate and one part of n-hexane.(S)-2-(isopropylsulfonyl)-amino-3-methyl-butyric acidN-[2-(3,4-dimethoxyphenyl)-ethyl]-amide, which can be further purifiedby recrystallization from methyl acetate/n-hexane, is obtained, meltingpoint 86°-87° C.

The compounds shown in Table 6 are obtained analogously to this example.

                  TABLE 6                                                         ______________________________________                                        (prepared according to process c))                                             ##STR24##                                                                    Comp.                                                                         No.    R.sub.1         R.sub.3  Physical data                                 ______________________________________                                        6.1    2-Propyl        2-Propyl m.p. 86-87° C.                         6.2    2-Butyl         2-Propyl m.p. 92-93° C.                         6.3    2-Butyl         2-Butyl  Resin                                         6.4    2-Methyl-propyl 2-Propyl m.p. 78-80° C.                         6.5    2-Methyl-propyl 2-Butyl  m.p. 74-76° C.                         6.6    Pentyl          2-Propyl m.p. 95-96° C.                         6.7    Pentyl          2-Butyl  m.p. 96-97° C.                         6.8    Hexyl           2-Propyl m.p. 102-103° C.                       6.9    Hexyl           2-Butyl  m.p. 102-103° C.                       6.10   Cyclohexyl      2-Propyl Resin                                         6.11   Cyclopentyl     2-Propyl Resin                                         6.12   Cyclopentyl     2-Butyl  Resin                                         6.13   Cyclohexyl      2-Butyl  Resin                                         6.14   2-(MeO-carbonyl)-ethyl                                                                        2-Propyl 98-99° C.                              ______________________________________                                         Stereochemistry on the α C atom of the amino acid: S               

PREPARATION EXAMPLE FOR INTERMEDIATES

Z-1.1: (S)-2-amino-3-methyl-butyric acidN-[2-(3,4-dimethoxyphenyl)-ethyl]-amide ##STR25##

23.8 g of (S)-2-[(1,1-dimethylethyl)-oxycarbonyl]-amino-3-methyl-butyricacid N-[2-(3,4-dimethoxyphenyl)]-ethyl-amide are stirred at roomtemperature together with 700 ml of 4N hydrochloric acid for 24 hours.The reaction mixture is extracted twice with 250 ml of ethyl acetateeach time; the organic phases are rinsed once with 200 ml of 2Nhydrochloric acid and then discarded. The combined aqueous phases arefirst brought to about pH 6 with solid sodium hydroxide and then broughtto pH greater than 8 with solid potassium carbonate. The aqueous phaseis subsequently saturated with sodium chloride and extracted twice with500 ml of ethyl acetate each time. The organic phases are rinsed oncewith 200 ml of saturated sodium chloride solution, combined, dried overpotassium carbonate and concentrated. (S)-2-amino-3-methyl-butyric acidN-[2-(3,4-dimethoxyphenyl)-ethyl]-amide, which can be purified byrecrystallization from ethyl acetate/hexane, is obtained; melting point52°-54° C.

The intermediates shown in Table 4 are obtained analogously to thisexample.

                  TABLE 4                                                         ______________________________________                                         ##STR26##                                                                    Comp.                                     Physical                            No.   R.sub.2                                                                             R.sub.3     R.sub.4                                                                           R.sub.5                                                                           R.sub.6   data                                ______________________________________                                        4.1   H     2-Propyl    H   H   3,4-Dimethoxy-                                                                          m.p.                                                                benzyl    52-54° C.                    4.2   H     2-Butyl     H   H   3,4-Dimethoxy-                                                                          m.p.                                                                benzyl    86-88° C.                    4.3   H     2-Methyl-   H   H   3,4-Dimethoxy-                                                                          m.p.                                            propyl              benzyl    70-72° C.                    4.4   H     2-Methylthio-                                                                             H   H   3,4-Dimethoxy-                                                                          Resin                                           ethyl               benzyl                                        4.5   H     Hydroxymethyl                                                                             H   H   3,4-Dimethoxy-                                                                benzyl                                        4.6   H     1-Hydroxy-  H   H   3,4-Dimethoxy-                                                                          m.p. 112-                                       ethyl               benzyl    113° C.                      ______________________________________                                         Stereochemistry on the α C atom of the amino acid: S               

Z-2.1 (R,S)-methanesulfonic acid N-(2-methyl-1-carboxy)-propyl-amide##STR27##

30 g of D,L-valine and 10.2 g of sodium hydroxide are dissolved in 250ml of water and the solution is cooled to 0° C., while stirring. Asolution of 10.2 g of sodium hydroxide in 250 ml of water and 20 ml ofmethanesulfonyl chloride in 250 ml of toluene are simultaneously addeddropwise to this solution during the course of, in each case, one hour.The reaction mixture is first further stirred at 0° C. for 2 hours andthen further stirred at room temperature for 16 hours. The toluene phaseis subsequently separated off in a separating funnel and discarded. Theaqueous phase is brought to pH less than 3 with concentratedhydrochloric acid. It is extracted twice with 1000 ml of diethyl ethereach time. The organic phases are washed twice with 200 ml of saturatedsodium chloride solution each time, combined, dried over magnesiumsulfate and concentrated. (R,S)-methanesulfonic acidN-(2-methyl-1-carboxy)-propyl-amide, which can be purified byrecrystallization from ethyl acetate/hexane, is obtained, melting point90°-91° C.

The intermediates shown in Table 5 are obtained analogously to thisexample.

                  TABLE 5                                                         ______________________________________                                         ##STR28##                                                                    Comp.                                                                         No.   R.sub.1    n     R.sub.2                                                                            R.sub.3 Physical data                             ______________________________________                                        5.1   Methyl     1     H    2-Propyl                                                                              m.p. 90-91° C.                     5.2   Methyl     1     H    2-Propyl                                                                              Oil                                       5.3   Me.sub.2 N 1     H    2-Propyl                                                                              Oil                                       5.4   Me.sub.2 N 1     H    2-Propyl                                                                              Resin                                     5.5   Methyl     0     H    2-Propyl                                          5.6   2-Propyl   0     H    2-Propyl                                          5.7   2-Methyl-2-                                                                              0     H    2-Propyl                                                propyl                                                                  5.8   Methyl     0     H    2-Propyl                                          5.9   2-Propyl   0     H    2-Propyl                                          5.10  2-Methyl-2-                                                                              0     H    2-Propyl                                                propyl                                                                  5.11  Ethyl      1     H    2-Propyl                                                                              Resin                                     5.12  Me.sub.2 N 1     H    2-Butyl Resin                                     5.13  Ethyl      1     H    1-(2-Me-2-                                                                            Oil                                                                   Pr)-O-ethyl                                       5.14  Methyl     1     H    Ethyl   Resin                                     5.15  Ethyl      1     H    Ethyl   Resin                                     5.16  Methyl     1     Me   Methyl  m.p. 109-111° C.                   5.17  Methyl     1     Tetramethylene                                                                           m.p. 133-135° C.                     ______________________________________                                         Stereochemistry disclosed on the α C atom of the amino acid:            R, S for compounds 5.1, 5.3, 5.5 to 5.7                                       S for compounds 5.2, 5.4, 5.8 to 5.15                                    

2. Formulation examples for active ingredients of the formula I(%=percent by weight)

    ______________________________________                                        F-2.1. Wettable powder                                                                              a)      b)      c)                                      ______________________________________                                        Active ingredient from Tables 1,2,3,3a                                                              25%     50%     75%                                     and 6                                                                         Sodium ligninsulfonate                                                                              5%      5%      --                                      Sodium laurylsulfate  3%      --       5%                                     Sodium diisobutylnaphthalenesulfonate                                                               --      6%      10%                                     Octylphenol polyethylene glycol ether                                                               --      2%      --                                      (7-8 mol of ethylene oxide)                                                   Highly disperse silicic acid                                                                        5%      10%     10%                                     Kaolin                62%     27%     --                                      ______________________________________                                    

The active ingredient is mixed thoroughly with the additives and themixture is ground thoroughly in a suitable mill. Wettable powders can bediluted with water to give suspensions of any desired concentration areobtained.

    ______________________________________                                        F-2.2. Emulsion concentrate                                                   ______________________________________                                        Active ingredient from Tables 1,2,3,3a                                                                   10%                                                and 6                                                                         Octylphenol polyethylene glycol ether                                                                    3%                                                 (4-5 mol of ethylene oxide)                                                   Calcium dodecylbenzenesulfonate                                                                          3%                                                 Castor oil polyglycol ether                                                                              4%                                                 (35 mol of ethylene oxide)                                                    Cyclohexanone              34%                                                Xylene mixture             50%                                                ______________________________________                                    

Emulsions of any desired concentration can be prepared from thisconcentrate by dilution with water.

    ______________________________________                                        F-2.3. Dust             a)     b)                                             ______________________________________                                        Active ingredient from Tables 1,2,3,3a                                                                 5%     8%                                            and 6                                                                         Talc                    95%    --                                             Kaolin                  --     92%                                            ______________________________________                                    

Ready-to-use dusts are obtained by mixing the active ingredient with thecarrier and grinding the mixture on a suitable mill.

    ______________________________________                                        F-2.4. Extruder granules                                                      ______________________________________                                        Active ingredient from Tables 1,2,3,3a                                                                10%                                                   and 6                                                                         Sodium ligninsulfonate  2%                                                    Carboxymethylcellulose  1%                                                    Kaolin                  87%                                                   ______________________________________                                    

The active ingredient is mixed with the additives and the mixture isground and moistened with water. This mixture is extruded and then driedin a stream of air.

    ______________________________________                                        F-2.5. Coated granules                                                        ______________________________________                                        Active ingredient from Tables 1,2,3,3a                                                                3%                                                    and 6                                                                         Polyethylene glycol (MW 200)                                                                          3%                                                    Kaolin                  94%                                                   ______________________________________                                         (MW = molecular weight)                                                  

The finely ground active ingredient is applied uniformly to the kaolin,which has been moistened with polyethylene glycol, in a mixer. Dust-freecoated granules are obtained in this manner.

    ______________________________________                                        F-2.6. Suspension concentrate                                                 ______________________________________                                        Active ingredient from Tables 1,2,3,3a                                                                40%                                                   and 6                                                                         Ethylene glycol         10%                                                   Nonylphenol polyethylene glycol ether                                                                 6%                                                    (15 mol of ethylene oxide)                                                    Sodium ligninsulfonate  10%                                                   Carboxymethylcellulose  1%                                                    37% aqueous formaldehyde solution                                                                     0.2%                                                  Silicone oil in the form of a                                                                         0.8%                                                  75% aqueous emulsion                                                          Water                   32%                                                   ______________________________________                                    

The finely ground active ingredient is mixed intimately with theadditives. A suspension concentrate from which suspensions of anydesired dilution can be prepared by dilution with water is thusobtained.

BIOLOGICAL EXAMPLES

B-1: Action against Plasmopara viticola on vines

a) Residual protective action

Vine seedlings in the 4-5 leaf stage are sprayed with a spray mixtureprepared from a wettable powder of the active ingredient (0.02% ofactive substance). After 24 hours, the treated plants are infected witha sporangia suspension of the fungus. After incubation for 6 days at95-100% relative atmospheric humidity and 20° C., the fungal infestationis evaluated.

Active ingredients No. 1.2, 3.1, 3.19, 3.25, 3.29 and others achievecomplete suppression of the fungal infestation (residual infestation 0to 10%). In contrast, untreated but infected control plants show aPlasmopara infestation of 100%.

B-2: Action against Phytophthora on tomato plants

a) Residual protective action

After growing for 3 weeks, tomato plants are sprayed with a spraymixture prepared from a wettable powder of the active ingredient (0.02%of active substance). After 48 hours, the treated plants are infectedwith a sporangia suspension of the fungus. The fungal infestation isevaluated after incubation of the infected plants for 4 days at 90-100%relative atmospheric humidity and 20° C.

b) Systemic action

After growing for three weeks, a spray mixture prepared from a wettablepowder of the active ingredient (0.02% of active substance, based on thesoil volume) is added to tomato plants. It is ensured that the spraymixture does not come into contact with the above-ground parts of theplant. After 4 days, the treated plants are infected with a sporangiasuspension of the fungus. The fungal infestation is evaluated afterincubation of the infected plants for 4 days at 90-100% relativeatmospheric humidity and 20° C.

Infestation is prevented practically completely (0 to 5% infestation)with compounds No. 3.1, 3.19, 3.25, 3.29 and others. In contrast,untreated but infected control plants show a Phytophthora infestation of100%.

B-3: Residual protective action against Cercospora arachidicola ongroundnuts

Groudnut plants 10 to 15 cm high are sprayed dripping wet with anaqueous spray mixture (0.02% of active substance) and infected with aconidia suspension of the fungus for 48 hours. The plants are incubatedfor 72 hours at 21 ° C. and high atmospheric humidity and then placed ina greeenhouse until the typical leaf spots appear. The action of theactive substance is evaluated 12 days after infection on the basis ofthe number and size of the leaf spots.

Active ingredients of the formula I cause a reduction in the leaf spotsto below about 10% of the leaf surface. The disease is completelysuppressed (0-5% infestation) in some cases.

B-4: Action against Puccinia graminis on wheat

a) Residual protective action

6 days after sowing, wheat plants are sprayed dripping wet with anaqueous spray mixture (0.02% of active substance), and infected 24 hourslater with a uredospore suspension of the fungus. After an incubationtime of 48 hours (conditions: 95-100% relative atmospheric humidity at20° C.), the plants are placed in a greenhouse at 22° C. The rustpustule development is evaluated 12 days after infection.

b) Systemic action

5 days after sowing, wheat plants are watered with an aqueous spraymixture (0.006% of active substance, based on the soil volume). It isensured that the spray mixture does not come into contact with theabove-ground parts of the plants. 48 hours later, the plants areinfected with a uredospore suspension of the fungus. After theincubation time of 48 hours (conditions: 95 to 100% relative atmospherichumidity at 20° C.), the plants are placed in a greenhouse at 22° C. Therust pustule development is evaluated 12 days after infection.

Compounds of the formula I cause a significant reduction in fungalattack, in some cases to 10-0%.

B-5: Residual protective action against Venturia inaequalis on apples

Apple seedlings with fresh shoots 10 to 20 cm long are sprayed dripingwet with a spray mixture (0.02% of active substance), and infected witha conidia suspension of the fungus 24 hours later. The plants areincubated for 5 days at 90-100% relative atmospheric humidity, andplaced in a greenhouse at 20°-24° C. for a further 10 days. The scabinfestation is evaluated 15 days after infection. Compounds of theformula I from one of the Tables 1, 2, 3, 3a and 6 chiefly display alasting action against scab diseases (less than 10% infestation).

B-6: Residual protective action agianst Erysiphe graminis on barley

Barley plants about 8 cm high are sprayed dripping wet with a spraymixture (0.02% of active substance) and dusted with conidia of thefungus 3 to 4 hours later. The infected plants are placed in agreenhouse at 22° C. The fungal attack is evaluated 10 days afterinfection.

Compounds of the formula I generally are capable of suppressing thedisease infestation to less than 20%, and in some cases also completely.

B-7: residual protective action against Botyris cinerea on apple fruit

Artificially damaged apples are treated by dripping a spray mixture(0.02% of active substance) onto the damaged areas. The treated fruit isthen inoculated with a spore suspension of the fungus and incubated forone week at high atmospheric humidity and 20° C. The fungicidal actionof the test substance is deduced from the number of superficially rotteddamaged areas. Active ingredients of the formula I from Tables 1, 2, 3,3a and 6 are capable of preventing the spread of the rot, in some casescompletely.

B-8: Action against Rhizoctonia solani on rice

a) Protective local soil application

Rice plants 10 days old are thoroughly watered with a suspension (spraymixture) prepared from the formulated test substance withoutabove-ground parts of the plants being contaminated. Infection iscarried out 3 days later by placing one barley straw infected withRhizoctonia solani between the flee plants per pot. After incubation ina climatically controlled room at a day-time temperature of 29° C. and anight-time temperature of 26° C. and 95% relative atmospheric humidityfor 6 days, the fungal infestation is evaluated. Less than 5% of therice plants showed an infestation. The plants had a healthy appearance.

b) Protective local leaf application

Rice plants 12 days old are sprayed with a suspension prepared from theformulated test substance. Infection is carried out one day later byplacing one barley straw infected with Rhizoctonia solani between therice plants per pot. After incubation in a climatically controlled roomat a day-time temperature of 29° C. and a night-time temperature of 26°C. and 95% relative atmospheric humidity for 6 days, rating is cardedout. Untreated but infected control plants show a fungal infestation of100%. Compounds of the formula I in some cases cause an almost completeinhibition of the disease infestation.

B-9: Action against Helminthosporium gramineum

Wheat grains are contaminated with a spore suspension of the fungus andleft to dry. The contaminated grains are dressed with a suspension ofthe test substance (600 ppm of active ingredient, based on the weight ofthe seeds). After 2 days, the grains are laid out on suitable agardishes, and after a further 4 days the development of the fungalcolonies around the grains is evaluated. The number and size of fungalcolonies are used to evaluate the test substance. Compounds of theformula I in some cases show a very good action, i.e. completeinhibition of the fungal colonies.

B-10: Action against Pythium debaryanum on sugar beet

The fungus is cultured from sterile oat grains and added to a soil/sandmixture. The soil thus infected is introduced into flowerpots and sownwith sugar beet seeds. Immediately after sowing, the test preparations,formulated as wettable powders, are poured over the soil as an aqueoussuspension (20 ppm of active ingredient, based on the soil volume). Thepots are then placed in a greenhouse at 20°-24° C. for 2-3 weeks. Thesoil is constantly kept uniformly moist by gentle spraying with water.For evaluation of the tests, the emergence of the sugar beet plants andthe proportion of healthy and sick plants are determined. Aftertreatment with active ingredients of the formula I, more than 80% of theplants emerge and have a healthy appearance. In the control pots, onlyisolated emerged plants with a sickly appearance are observed.

What is claimed is:
 1. A compound of the formula I ##STR29## in which nis the number zero or one;R₁ is C₁ -C₁₂ alkyl, which is unsubstituted orcan be substituted by C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁ -C₄alkylsulfonyl, C₃ -C₈ cycloalkyl, cyano, C₁ -C₆ alkoxycarbonyl, C₃ -C₆alkenyloxycarbonyl or C₃ -C₆ alkynyloxycarbonyl; C₃ -C₈ cycloalkyl; C₂-C₂ alkenyl; C₂ -C₁₂ alkynyl; C₁ -C₁₂ halogenoalkyl or a group NR₁₃ R₁₄; in which R₁₃ and R₁₄ independently of one another are hydrogen or C₁-C₆ alkyl or together are tetra- or pentamethylene; R₂ and R₃independently of one another are hydrogen; C₁ -C₈ alkyl; C₁ -C₈ alkylwhich is substituted by hydroxyl, C₁ -C₄ alkoxy, mercapto or C₁ -C₄alkylthio; C₃ -C₈ alkenyl; C₃ -C₈ alkynyl; C₃ -C₈ cycloalkyl or C₃ -C₈cycloalkyl-C₁ -C₄ alkyl, or in which the two groups R₂ and R₃, togetherwith the carbon atom to which they are bonded, form a three- toeight-membered carbocyclic ring; R₄ is hydrogen or C₁ -C₆ alkyl; R₅ ishydrogen; C₁ -C₆ alkyl or phenyl, which is unsubstituted or can besubstituted by halogen, nitro, C₁ -C₄ alkyl, C₁ -C₄ halogenoalkyl, C₁-C₄ alkoxy or C_(1-C) ₄ alkylthio; and R₆ is a group G ##STR30## inwhich R₇ and R₈ independently of one another are hydrogen or C₁ -C₆alkyl; p is the number zero or one; and R₉, R₁₀ and R₁₁ independently ofone another are hydrogen, C₁ -C₆ alkyl, C₁ -C₆ halogenoalkyl, C₃ -C₆alkenyl, C₃ -C₆ alkynyl, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆alkynyloxy, C₁ -C₆ alkylthio, halogen or nitro.
 2. A compound of theformula I ##STR31## in which n is the number zero or one;R₁ is C₁ -C₁₂alkyl; C₁ -C₁₂ alkyl which is substituted by C₁ -C₄ alkoxy, C₁ -C₄alkylthio or C₁ -C₄ alkylsulfonyl; C₂ -C₁₂ alkenyl; C₂ -C₁₂ alkynyl; C₁-C₁₂ halogenoalkyl or a group NR₁₃ R₁₄ ; in which R₁₃ and R₁₄independently of one another are C₁ -C₆ alkyl or together are tetra- orpentamethylene; R₂ and R₃ independently of one another are hydrogen; C₁-C₈ alkyl; C₁ -C₈ alkyl which is substituted by hydroxyl, C₁ -C₄ alkoxy,mercapto or C₁ -C₄ alkylthio; C₃ -C₈ alkenyl; C₃ -C₈ alkynyl; C₃ -C₈cycloalkyl; or C₃ -C₈ cycloalkyl-C₁ -C₄ alkyl, or in which the twogroups R₂ and R₃, together with the carbon atom to which they arebonded, form a three- to eight-membered carbocyclic ring; R₄ is hydrogenor C₁ -C₆ alkyl; R₅ is hydrogen; C₁ -C₆ alkyl or phenyl, which isunsubstituted or substituted by halogen, nitro, C₁ -C₄ alkyl, C₁ -C₄halogenoalkyl, C₁ -C₄ alkoxy or C₁ -C₄ alkylthio; and R₆ is a group G:##STR32## in which R₇ and R₈ independently of one another are hydrogenor C₁ -C₆ alkyl; p is the number zero or one; and R₉, R₁₀ and R₁₁independently of one another are hydrogen, C₁ -C₆ alkyl, C₁ -C₆halogenoalkyl, C₃ -C₆ alkenyl, C₃ -C₆ alkynyl, C₁ -C₆ alkoxy, C₃ -C₆alkenyloxy, C₃ -C₆ alkynyloxy, C₁ -C₆ alkylthio, halogen or nitro.
 3. Acompound according to claim 2, in whichR₁ is C₁ -C₁₂ alkyl; C₁ -C₁₂alkyl which is substituted by C₁ -C₄ alkoxy, C₁ -C₄ alkylthio or C₁ -C₄alkylsulfonyl; C₂ -C₁₂ alkenyl; C₁ -C₁₂ halogenoalkyl or a group NR₁₃R₁₄ ; in which R₁₃ and R₁₄ independently of one another are C₁ -C₆alkyl, or together are tetra- or pentamethylene; R₂ is hydrogen; R₃ isC₁ -C₈ alkyl; C₁ -C₈ alkyl which is substituted by hydroxyl, C₁ -C₄alkoxy, mercapto or C₁ -C₄ alkylthio; or C₃ -C₈ cycloalkyl; R₄ ishydrogen; R₅ is phenyl, which is unsubstituted or substituted byhalogen, nitro, C₁ -C₄ alkyl, C₁ -C₄ halogenoalkyl, C₁ -C₄ alkoxy or C₁-C₄ alkylthio and R₆ is a group G in which p is the number zero; and R₉,R₁₀ and R₁₁ independently of one another are hydrogen, C₁ -C₆ alkyl, C₁-C₆ halogenoalkyl, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy,halogen or nitro.
 4. A compound according to claim 1, in whichn is thenumber zero or one; R₁ is C₁ -C₁₀ alkyl; C₁ -C₄ halogenoalkyl; C₂ -C₆alkenyl; C₅ -C₆ cycloalkyl; C₁ -C₆ alkyl which is substituted by cyanoor C₁ -C₄ alkoxycarbonyl, or C₁ -C₂ dialkylamino; R₂ is hydrogen; R₃ isC₂ -C₅ alkyl or C₃ -C₆ cycloalkyl; R₄ is hydrogen; R₅ is phenyl, whichis unsubstituted or substituted by halogen; and R₆ is a group G, inwhich p is the number zero; R₉ is hydrogen; and R₁₀ and R₁₁independently of one another are hydrogen or halogen.
 5. A compoundaccording to claim 2, in whichn is the number zero or one; R₁ is C₁ -C₁₀alkyl; C₁ -C₄ halogenoalkyl; C₂ -C₆ alkenyl, or C₁ -C₂ dialkylamino; R₂is hydrogen; R₃ is C₂ -C₅ alkyl or C₃ -C₆ cycloalkyl; R₄ is hydrogen; R₅is phenyl, which is unsubstituted or substituted by halogen; and R₆ is agroup G in which p is the number zero; R₉ is hydrogen; and R₁₀ and R₁₁independently of one another are hydrogen or halogen.
 6. A compoundaccording to claim 5, in whichn has the value one.
 7. A compoundaccording to claim 5, in whichn has the value one; and R₁ is methyl,ethyl, vinyl or dimethylamino.
 8. A compound according to claim 4, inwhichn has the value one; and R₁ is methyl, ethyl, vinyl, cyclopentyl,cyclohexyl or dimethylamino.
 9. A compound according to claim 5, inwhichn has the value one; and R₃ is C₃ -C₄ alkyl.
 10. A compoundaccording to claim 1, in whichR₁ is C₁ -C₁₂ alkyl; C₃ -C₈ cycloalkyl; C₁-C₁₂ alkyl which is substituted by C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, C₁-C₄ alkylsulfonyl, C₃ -C₈ cycloalkyl, cyano, C₁ -C₆ alkoxycarbonyl, C₃-C₆ alkenyloxycarbonyl or C₁ -C₆ alkynyloxycarbonyl; C₂ -C₁₂ alkenyl; C₁-C₁₂ halogenoalkyl or a group NR₁₃ R₁₄ ; in which R₁₃ and R₁₄independently of one another are hydrogen or C₁ -C₆ alkyl or togetherare tetra- or pentamethylene; R₂ is hydrogen; R₃ is C₁ -C₈ alkyl; C₁ -C₈alkyl which is substituted by hydroxyl, C₁ -C₄ alkoxy, mercapto or C₁-C₄ alkylthio; or C₃ -C₈ cycloalkyl; R₄ is hdyrogen or C₁ -C₄ alkyl; R₅is hydrogen; or C₁ -C₆ alkyl; and R₆ is a group G in which R₇ and R₈independently of one another are hydrogen or C₁ -C₄ alkyl; p is thenumber one; and R₉, R₁₀ and R₁₁ independently of one another arehydrogen, C₁ -C₆ alkyl, C₁ -C₆ halogenoalkyl, C₁ -C₆ alkoxy, C₃ -C₆alkenyloxy, C₃ -C₆ alkynyloxy or halogen.
 11. A compound according toclaim 2, in whichR₁ is C₁ -C₁₂ alkyl; C₁ -C₁₂ alkyl which is substitutedby C₁ -C₄ alkoxy, C₁ -C₄ alkylthio or C₁ -C₄ alkylsulfonyl; C₂ -C₁₂alkenyl; C₁ -C₁₂ halogenoalkyl or a group NR₁₃ R₁₄ ; in which R₁₃ andR₁₄ independently of one another are C₁ -C₆ alkyl or together are tetra-or pentamethylene; R₂ is hydrogen; R₃ is C₁ -C₈ alkyl; C₁ -C₈ alkylwhich is substituted by hydroxyl, C₁ -C₄ alkoxy, mercapto or C₁ -C₄alkylthio; or C₃ -C₈ cycloalkyl; R₄ is hydrogen or C₁ -C₄ alkyl; R₅ ishydrogen or C₁ -C₆ alkyl; and R₆ is a group G in which R₇ and R₈independently of one another are hydrogen or C₁ -C₄ alkyl; p is thenumber one; and R₉, R₁₀ and R₁₁ independently of one another arehydrogen, C₁ -C₆ alkyl, C₁ -C₆ halogenoalkyl, C₁ -C₆ alkoxy, C₃ -C₆alkenyloxy, C₃ -C₆ alkynyloxy or halogen.
 12. A compound according toclaim 2, in whichn is the number zero or one; R₁ is C₁ -C₁₀ alkyl, C₁-C₄ halogenoalkyl, C₂ -C₆ alkenyl or C₁ -C₂ dialkylamino; R₂ ishydrogen; R₃ is C₂ -C₅ alkyl or C₃ -C₆ cycloalkyl; R₄ is hydrogen or C₁-C₄ alkyl; R₅ is hydrogen; and R₆ is a group G in which R₇ is hydrogen;R₈ is hydrogen or C₁ -C₄ alkyl; p is the number one; and R₉, R₁₀ and R₁₁independently of one another are hydrogen, C₁ -C₆ alkyl, C₁ -C₆halogenoalkyl, C₁ -C₆ alkoxy, C₃ -C₆ alkenyloxy, C₃ -C₆ alkynyloxy orhalogen.
 13. A compound according to claim 12, in whichn is the numberone; R₁ is C₁ -C₁₀ alkyl, C₁ -C₄ halogenoalkyl, C₂ -C₄ alkenyl or C₁ -C₂dialkylamino; R₉ is hydrogen; and R₁₀ and R₁₁ are C₁ -C₆ alkoxy.
 14. Acompound according to claim 13, in whichR₁ is C₁ -C₄ alkyl; C₁ -C₄halogenoalkyl, vinyl or dimethylamino.
 15. A compound according to claim13, in whichR₃ is C₃ -C₄ alkyl.
 16. A compound according to claim 13, inwhichR₄ is hydrogen; and R₈ is hydrogen.
 17. A compound according toclaim 13, in whichR₁₀ is p-C₁ -C₄ alkoxy; and R₁₁ is m-C₁ -C₄ alkoxy.18. A compound according to claim 17, in whichR₁ is C₁ -C₄ alkyl, vinylor dimethylamino; R₁₀ is p-methoxy; and R₁₁ is m-methoxy.
 19. A compoundaccording to claim 1, in whichn is the number one; and R₁ is C₁ -C₁₀alkyl; C₁ -C₄ halogenoalkyl; C₂ -C₄ alkenyl; C₅ -C₆ cycloalkyl; C₁ -C₄alkyl which is substituted by cyano or C₁ -C₄ alkoxycarbonyl, or C₁ -C₂dialkylamino; R₉ is hydrogen; and R₁₀ and R₁₁ are C₁ -C₆ alkoxy, C₃ -C₆alkenyloxy or C₃ -C₆ alkynyloxy.
 20. A compound according to claim 19,in whichR₁ is C₁ -C₄ alkyl, C₁ -C₄ halogenoalkyl, vinyl, dimethylaminoor C₅ -C₆ cycloalkyl.
 21. A compound according to claim 19, in whichR₃is C₃ -C₄ alkyl.
 22. A compound according to claim 19, in whichR₁₀ isp-C₁ -C₄ alkoxy, p-C₃ -C₄ alkenyloxy or p-C₃ -C₄ alkynyloxy; and R₁₁ ism-C₁ -C₄ alkoxy.
 23. A compound according to claim 22, in whichR₁ is C₁-C₄ alkyl, vinyl or dimethylamino; R₁₀ is p-methoxy, p-allyloxy orp-propargyloxy; and R₁₁ is m-methoxy.
 24. A compound according to claim23, in whichR₁₀ is p-methoxy and R₁₁ is m-methoxy.